EP1242506A1 - Method for the production of polyamides - Google Patents

Method for the production of polyamides

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Publication number
EP1242506A1
EP1242506A1 EP00990757A EP00990757A EP1242506A1 EP 1242506 A1 EP1242506 A1 EP 1242506A1 EP 00990757 A EP00990757 A EP 00990757A EP 00990757 A EP00990757 A EP 00990757A EP 1242506 A1 EP1242506 A1 EP 1242506A1
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EP
European Patent Office
Prior art keywords
reaction
water
stage
reaction stage
pressure
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Granted
Application number
EP00990757A
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German (de)
French (fr)
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EP1242506B1 (en
Inventor
Ralf Mohrschladt
Helmut Winterling
Dieter Krauss
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes

Definitions

  • the present invention relates to a process for the preparation of polyamides from aminonitriles and water.
  • the reaction of aminonitriles with water to produce polyamides is known, for example, from DE-A-197 09 390.
  • Water / aminonitrile reaction mixtures are reacted in a multi-stage process at high temperatures and pressures in the presence of heterogeneous metal oxide fixed bed catalysts.
  • the catalyst used improves the viscosity build-up and increases the number of carboxyl end groups in the polyamide.
  • the catalyst can be separated from the reaction product so that the product properties are not adversely affected by it.
  • the object of the present invention is to provide a process for the preparation of polyamides from aminonitriles and water which requires fewer reaction stages and an improved space-time yield having.
  • the process can also preferably lead to an increased carboxyl end group content in the product.
  • the object is achieved according to the invention by a process for the preparation of polyamides from aminonitriles and water
  • the reaction in the first reaction stage is carried out in the presence of heterogeneous catalysts.
  • the reaction in the first reaction stage is carried out in the absence of a catalyst, but a further reaction stage is provided between the first reaction stage and the relaxation, in which the reaction mixture obtained in the first reaction stage in the presence of heterogeneous catalysts a temperature in the range of 200 to 320 ° C and a pressure at which the reaction mixture is in single phase liquid is reacted.
  • the embodiments thus comprise 2 or 3 process stages, which can be operated continuously or discontinuously.
  • known metal oxides such as zirconium oxide, aluminum oxide, magnesium oxide, cerium oxide, lanthanum oxide and preferably titanium dioxide as well as beta-zeolites and layered silicates can be used as catalysts for heterogeneous catalysis.
  • Titanium dioxide in the so-called anatase modification is particularly preferred.
  • the titanium dioxide is preferably present in the anatase modification to an extent of at least 70% by weight, particularly preferably at least 90%, in particular essentially completely.
  • silica gel, zeolites and doped metal oxides for example ruthenium, copper or fluoride being used for doping, significantly improve the conversion of the starting materials mentioned.
  • Suitable catalysts are distinguished in particular by the fact that they are slightly Bronsted acid and have a large specific surface area.
  • the heterogeneous catalyst has a macroscopic shape which enables the polymer melt to be mechanically separated from the catalyst, for example by means of screens or filters.
  • the catalyst can be used in the form of strand pellets or as a coating on packing.
  • the process according to the invention is characterized by different reaction zones: the reaction of aminonitrile with water (1) takes place in a first reaction stage (3) at a temperature of 180 to 350 ° C., preferably 230 to 290 ° C.
  • the pressure is selected so that in addition to a liquid phase there is a gas phase which contains ammonia and water in particular and can be separated off via a column (4).
  • the pressure is particularly preferably set so that the water content in the reaction mixture remains constant and the largest possible amounts of ammonia can be removed from the gas phase.
  • water is continuously added to the reaction mixture in the reaction stage (2) and removed again via the gas phase or via the column (4).
  • the reaction stage therefore has high pressures between 30 and 120 bar.
  • the reaction volume contains heterogeneous metal oxide catalysts or internals (5, 6) which are coated with the metal oxide catalyst. If desired, the reaction zones through which water flows continuously are spatially separated from the reaction zones which contain the catalyst material. Transfer from the high pressure to the low pressure stage (separator or polycondensation stage)
  • the pressurized reaction mixture is then expanded adiabatically or via an evaporator zone into a polycondensation stage (8).
  • the adiabatic relaxation is preferably used when the water content of the reaction mixture is not more than 10% by weight, based on the total mass.
  • the use of an evaporator zone (7) is advantageous.
  • the volatile, low-molecular components such as water and ammonia present in the reaction mixture can pass into the gas phase there.
  • the evaporation zone ensures a sufficient heat input into the reaction mixture, so that the cooling of the mixture which begins due to water evaporation can be compensated for.
  • the temperatures in the evaporator zone are 230 to 320 ° C., preferably 250 to 290 ° C., the residence time is usually less than 5 minutes and is preferably less than 60 seconds.
  • the evaporator zone is advantageously designed as a tube bundle (7), the tubes optionally having periodically recurring cross-sectional constrictions in the axial direction.
  • the reaction mixture is preferably passed into a mass transfer zone, the pressure and temperature conditions of the evaporation zone being maintained.
  • the mass transfer between the liquid and gaseous phases can continue here and the ammonia separation can be improved.
  • the tubular mass transfer zone contains internals, for example fillers such as Raschig rings, metal rings and fillers made of wire mesh, in order to provide a large surface area.
  • Other known evaporator apparatuses such as circulation evaporators and thin-film evaporators, for example film extruders or annular disk reactors, can also be used as mass transfer zones.
  • the packing is coated with the above-mentioned catalyst components, or catalyst granules are used directly as packing.
  • the conversion of nitrile and acid amide groups in the reaction mixture can be decisively improved in this way. postcondensation
  • the product obtained after the expansion or after evaporation in the evaporator zone is subjected to post-polymerization or condensation in at least one subsequent reaction stage (8), the so-called separator or polycondensation stage, which, if desired, also contains heterogeneous catalysts optionally under reduced pressure, according to known methods.
  • the pressure in this separation zone is generally in the range from 0.1 mbar to 5 bar, preferably in the range from 100 to 1500 mbar, the temperature in the melt is 230 to 320, preferably 240 to 290 and particularly preferably 250 to 270 ° C.
  • the components released here in the gas phase are advantageously rectified together with the vapors from the evaporation and mass transfer zone in a column (9).
  • the column can be operated, for example, under the same pressure conditions as the evaporator zone.
  • the rectified ammonia and water vapors are removed at the top of the column and condensed.
  • the water obtained, like the low molecular weight constituents or oligomers deposited in the column bottom, can be fed (returned) to the educt stream.
  • the amino nitrile / water mixture is implemented analogously to the two-stage embodiment in a first stage (3), which corresponds to the above description.
  • This stage is preferably operated in the three-stage embodiment, however, without the use of a catalyst bed.
  • the catalyst bed is located in a downstream second reaction stage (13), for example a tubular reactor, in which the pressure is adjusted so that the reaction mixture is in a single-phase liquid. It is advantageous to use a pump (12) to introduce the reaction mixture into the tubular reactor, to guarantee the single phase of the system.
  • the temperatures in the tubular reactor are 200 to 320 ° C, preferably 210 to 290 ° C and particularly preferably 220 to 260 ° C.
  • the product from the second stage is then again transferred, analogously to the two-stage embodiment, either adiabatically or via evaporator and mass transfer zones (7) to a third stage (8) for water separation and post-condensation.
  • Pigments such as titanium dioxide, silicon dioxide or talc, chain regulators such as aliphatic and aromatic carboxylic and dicarboxylic acids such as propionic acid or terephthalic acid, stabilizers such as copper (I) halides and alkali metal halides, nucleating agents such as magnesium silicate can be used as customary additives and fillers or boron nitride, catalysts, such as phosphorous acid, and antioxidants in amounts in the range from 0 to 5% by weight, preferably from 0.05 to 1% by weight, based on the total amount of monomers.
  • the additives are generally added before the granulation and before, during or after, preferably after the polymerization.
  • the additives are particularly preferably added to the reaction mixture only after passing through the reaction zones which contain the heterogeneous catalysts.
  • the polymer (11) obtained according to the invention can then be processed further by customary processes, for example it can be made into pieces by customary methods by discharging it in the form of melt profiles, then passing it through a water bath and cooling it and then granulating it.
  • the granules can then be extracted by methods known per se and subsequently or simultaneously converted into high molecular weight polylactam.
  • the extraction can be carried out, for example, with water or an aqueous caprolactam solution. consequences.
  • Another possibility is gas phase extraction, as described for example in EP-A-0284 968.
  • the desired viscosity number of the end product is usually in the range from 120 to 350 ml / g. It can be set in a manner known per se.
  • RV relative viscosity
  • 100 parts by weight of polymer are stirred or extracted with 400 parts by weight of deionized water at 100 ° C. for 32 hours under reflux and, after removal of the water, mild, i.e. without the risk of post-condensation, dried at a temperature of 100 ° C for a period of 20 hours in a vacuum.
  • Process examples 1, 2, 3 and 4 were carried out batchwise in an 11-autoclave. 1st process stage (high pressure)
  • the autoclave is closed, vented and flushed several times with nitrogen.
  • water is continuously fed to the reaction mixture through the discharge opening of the boiler with the aid of a piston pump.
  • a valve on the vapor line regulates the internal boiler pressure. The upper part of the reaction volume is stirred.
  • the water supply is interrupted and the pressure and the temperature in the reactor are reduced or set to the required values for post-condensation within 30 to 60 minutes.
  • the polymer melt can be drawn out in a strand in a water bath, granulated and dried.
  • catalyst granules made from Finnti titanium dioxide, type S150, with a diameter of 4 mm and a length between 5 and 20 mm are used.
  • the titanium dioxide is present in the anatase modification and is fixed in the autoclave with the aid of sieves or separated from the emerging product stream.
  • VWD residence time TiO 2 : granules of titanium dioxide * molar ACN / water ratio RV: relative viscosity

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for the production of polyamides from amino nitriles and water, (1) by reacting aminonitriles with water at a temperature of 180 - 350 °C and a pressure of 30 - 120 bar adjusted in such a way that in addition to a liquid phase, a gaseous phase is also present in the first reaction step; (2) relaxation of the reaction mixture obtained in the first reaction step via an evaporator zone or adiabatically with removal of water and ammonia in a second reaction step and (3) post-condensation in the second reaction step at a pressure 0.1 mbar to 5 bar at a temperature of 230 - 320 °C.

Description

Verfahren zur Herstellung von Polyamiden Process for the production of polyamides
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Polyamiden aus Aminonitrilen und Wasser.The present invention relates to a process for the preparation of polyamides from aminonitriles and water.
Die Umsetzung von Aminonitrilen mit Wasser zur Herstellung von Polyamiden ist beispielsweise aus DE-A-197 09 390 bekannt. Dabei werden Wasser/Aminonitril-Reaktionsgemische in einem mehrstufigen Verfahren bei hohen Temperaturen und Drücken in Gegenwart von heterogenen Metalloxid- Festbettkatalysatoren umgesetzt. Durch den eingesetzten Katalysator werden der Viskositätsaufbau verbessert und die Carboxylendgruppenzahl im Polyamid erhöht. Der Katalysator kann dabei vom Reaktionsprodukt abgetrennt werden, so daß die Produkteigenschaften durch ihn nicht negativ beeinflußt werden.The reaction of aminonitriles with water to produce polyamides is known, for example, from DE-A-197 09 390. Water / aminonitrile reaction mixtures are reacted in a multi-stage process at high temperatures and pressures in the presence of heterogeneous metal oxide fixed bed catalysts. The catalyst used improves the viscosity build-up and increases the number of carboxyl end groups in the polyamide. The catalyst can be separated from the reaction product so that the product properties are not adversely affected by it.
Im Vergleich zu konventionell aus Caprolactam polymerisierten Polyamiden ist die Carboxylendgruppenzahl eines aus Aminocapronitril (ACN) hergestellten Polyamids häufig signifikant geringer. Häufig sind zudem lange Gesamtverweildauern der Reaktionsmischung bis zum Erhalt einer Präpolymerschmelze, die granuliert, extrahiert und getrocknet werden kann, erforderlich. Hierdurch und durch die große Zahl der Reaktionsstufen ist das Verfahren nicht immer wirtschaftlich vorteilhaft oder mit höheren Investitionskosten verbunden.Compared to polyamides polymerized conventionally from caprolactam, the number of carboxyl end groups of a polyamide made from aminocapronitrile (ACN) is often significantly lower. In addition, long total residence times of the reaction mixture are often required until a prepolymer melt is obtained, which can be granulated, extracted and dried. This and the large number of reaction stages mean that the process is not always economically advantageous or involves higher investment costs.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines Verfahrens zur Herstellung von Polyamiden aus Aminonitrilen und Wasser, das mit einer geringeren Reaktionsstufenzahl auskommt und eine verbesserte Raum-Zeit-Ausbeute aufweist. Das Verfahren kann zudem vorzugsweise zu einem erhöhten Carboxylendgruppengehalt im Produkt führen.The object of the present invention is to provide a process for the preparation of polyamides from aminonitriles and water which requires fewer reaction stages and an improved space-time yield having. The process can also preferably lead to an increased carboxyl end group content in the product.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Herstellung von Polyamiden aus Aminonitrilen und Wasser durchThe object is achieved according to the invention by a process for the preparation of polyamides from aminonitriles and water
(1) Umsetzung von Aminonitrilen mit Wasser bei einer Temperatur im Bereich von 180 bis 350°C und einem Druck im Bereich von 30 bis 120 bar, der so eingestellt wird, daß neben einer flüssigen Phase eine gasförmige Phase vorliegt, in einer ersten Reaktionsstufe,(1) reaction of aminonitriles with water at a temperature in the range from 180 to 350 ° C. and a pressure in the range from 30 to 120 bar, which is adjusted so that a gaseous phase is present in addition to a liquid phase, in a first reaction stage,
(2) Entspannung des in der ersten Reaktionsstufe erhaltenen Reaktionsgemisches über eine Verdampferzone oder adiabatisch unter Entfernung von Wasser und Ammoniak in eine zweite Reaktionsstufe und(2) Relaxation of the reaction mixture obtained in the first reaction stage via an evaporator zone or adiabatically with removal of water and ammonia in a second reaction stage and
(3) Nachkondensation in der zweiten Reaktionsstufe bei einem Druck im Be- reich von 0,1 mbar bis 5 bar und einer Temperatur im Bereich 230 bis(3) Post-condensation in the second reaction stage at a pressure in the range from 0.1 mbar to 5 bar and a temperature in the range from 230 to
320°C.320 ° C.
Gemäß einer Ausführungsform der Erfindung wird dabei die Umsetzung in der ersten Reaktionsstufe in Gegenwart von heterogenen Katalysatoren durchgeführt.According to one embodiment of the invention, the reaction in the first reaction stage is carried out in the presence of heterogeneous catalysts.
Gemäß einer weiteren Ausfuhrungsform der Erfindung wird die Umsetzung in der ersten Reaktionsstufe in Abwesenheit eines Katalysators durchgeführt, dafür jedoch zwischen der ersten Reaktionsstufe und der Entspannung eine weitere Reaktionsstufe vorgesehen, in der das in der ersten Reaktionsstufe erhaltene Reak- tionsgemisch in Gegenwart von heterogenen Katalysatoren bei einer Temperatur in Bereich von 200 bis 320 °C und einem Druck, bei dem das Reaktionsgemisch einphasig-flüssig vorliegt, umgesetzt wird.According to a further embodiment of the invention, the reaction in the first reaction stage is carried out in the absence of a catalyst, but a further reaction stage is provided between the first reaction stage and the relaxation, in which the reaction mixture obtained in the first reaction stage in the presence of heterogeneous catalysts a temperature in the range of 200 to 320 ° C and a pressure at which the reaction mixture is in single phase liquid is reacted.
Die Ausfuhrungsformen umfassen somit 2 oder 3 Verfahrensstufen, die kontinuierlich oder diskontinuierlich betrieben werden können.The embodiments thus comprise 2 or 3 process stages, which can be operated continuously or discontinuously.
Beiden Ausfuhrungsformen gemein ist, daß in einer ersten Verfahrensstufe Ami- nonitrile mit Wasser in einem Reaktor umgesetzt werden, der neben einer flüssi- gen Phase, dem Reaktionsgemisch, eine Gasphase enthält, und daß die Komponenten der Gasphase über eine Kolonne von der flüssigen Phase abgetrennt werden können.It is common to both embodiments that in a first process stage, aminonitriles are reacted with water in a reactor which, in addition to a liquid gene phase, the reaction mixture contains a gas phase, and that the components of the gas phase can be separated from the liquid phase via a column.
Erfindungsgemäß können als Katalysatoren zur heterogenen Katalyse bekannte Metalloxide, wie Zirkonoxid, Aluminiumoxid, Magnesiumoxid, Ceroxid, Lanthanoxid und bevorzugt Titandioxid wie auch Beta-Zeolithe und Schichtsilikate eingesetzt werden. Besonders bevorzugt ist Titandioxid in der sogenannten Anatas-Modifikation. Vorzugsweise liegt das Titandioxid zu mindestens 70 Gew.- %, besonders bevorzugt mindestens 90%, inbesondere im wesentlichen vollständig in der Anatas-Modifikation vor. Des weiteren wurde gefunden, daß auch Kieselgel, Zeolithe und dotierte Metalloxide, wobei zum Beispiel Ruthenium, Kupfer oder Fluorid zur Dotierung eingesetzt werden, die Umsetzung der genannten Edukte deutlich verbessern. Geeignete Katalysatoren zeichnen sich insbesondere dadurch aus, daß sie leicht Brönsted-sauer sind und eine große spezifische Oberfläche besitzen. Erfindungsgemäß weist der heterogene Katalysator eine makroskopische Form auf, die eine mechanische Abtrennung der Polymerschmelze vom Katalysator, beispielsweise durch Siebe oder Filter, ermöglicht. Beispielsweise kann der Katalysator in Strang-Granulat-Form oder als Beschichtung auf Füllkör- pern eingesetzt werden.According to the invention, known metal oxides such as zirconium oxide, aluminum oxide, magnesium oxide, cerium oxide, lanthanum oxide and preferably titanium dioxide as well as beta-zeolites and layered silicates can be used as catalysts for heterogeneous catalysis. Titanium dioxide in the so-called anatase modification is particularly preferred. The titanium dioxide is preferably present in the anatase modification to an extent of at least 70% by weight, particularly preferably at least 90%, in particular essentially completely. Furthermore, it was found that silica gel, zeolites and doped metal oxides, for example ruthenium, copper or fluoride being used for doping, significantly improve the conversion of the starting materials mentioned. Suitable catalysts are distinguished in particular by the fact that they are slightly Bronsted acid and have a large specific surface area. According to the invention, the heterogeneous catalyst has a macroscopic shape which enables the polymer melt to be mechanically separated from the catalyst, for example by means of screens or filters. For example, the catalyst can be used in the form of strand pellets or as a coating on packing.
Die beiden Ausführungsformen gemäß der vorliegenden Erfindung werden nachstehend anhand der Zeichnung näher erläutert.The two embodiments according to the present invention are explained below with reference to the drawing.
Dabei zeigen Figur 1 und Figur 2 schematisch die beiden Ausführungsformen gemäß der Erfindung. Die Bezugszeichen haben folgende Bedeutung:1 and 2 show schematically the two embodiments according to the invention. The reference symbols have the following meaning:
1 : A_minonitrilzuführung1: A_minonitrile feed
2: Wasserzuführung2: water supply
3: erste Reaktionsstufe3: first reaction stage
4: Kolonne4: column
5,6: Einbauten, die mit dem Katalysator beschichtet sind 7 Verdampferzone5,6: internals coated with the catalyst 7 evaporator zone
8 Polykondensationsstufe8 polycondensation stage
9 Kolonne9 column
10 Pumpe10 pump
11 ausgetragenes Polyamid11 discharged polyamide
12 Pumpe12 pump
13 zweite Reaktionsstufe13 second reaction stage
Zweistufige Ausführungsform (siehe Figur 1)Two-stage embodiment (see Figure 1)
Das erfindungsgemäße Verfahren ist durch verschiedene Reaktionszonen gekennzeichnet: Die Umsetzung von Aminonitril mit Wasser (1) erfolgt in einer ersten Reaktionsstufe (3) bei einer Temperatur von 180 bis 350°C, bevorzugt 230 bis 290°C. Der Druck ist so gewählt, daß neben einer flüssigen Phase eine Gasphase vorliegt, die insbesondere Ammoniak und Wasser enthält und über eine Kolonne (4) abgetrennt werden kann. Besonders bevorzugt wird der Druck so eingestellt, daß der Wassergehalt im Reaktionsgemisch konstant bleibt und möglichst große Mengen Ammoniak der Gasphase entzogen werden können. In einer bevorzugten Ausführungsform wird dem Reaktionsgemisch in der Reaktionsstufe kontinuierlich Wasser zugeführt (2) und über die Gasphase bzw. über die Kolonne (4) wieder entzogen. Die Reaktionsstufe weist deshalb hohe Drücke zwischen 30 und 120 bar auf.The process according to the invention is characterized by different reaction zones: the reaction of aminonitrile with water (1) takes place in a first reaction stage (3) at a temperature of 180 to 350 ° C., preferably 230 to 290 ° C. The pressure is selected so that in addition to a liquid phase there is a gas phase which contains ammonia and water in particular and can be separated off via a column (4). The pressure is particularly preferably set so that the water content in the reaction mixture remains constant and the largest possible amounts of ammonia can be removed from the gas phase. In a preferred embodiment, water is continuously added to the reaction mixture in the reaction stage (2) and removed again via the gas phase or via the column (4). The reaction stage therefore has high pressures between 30 and 120 bar.
Erfindungsgemäß enthält das Reaktionsvolumen heterogene Metalloxidkatalysa- toren oder Einbauten (5, 6), die mit dem Metalloxidkatalysator beschichtet sind. Gewünschtenfalls sind die Reaktionszonen, die kontinuierlich vom Wasser durchströmt werden, räumlich von den Reaktionszonen, die das Katalysatormaterial enthalten, getrennt. Überführung von der Hochdruck- in die Niederdruckstufe (Abscheider- bzw. Polykondensationsstufe)According to the invention, the reaction volume contains heterogeneous metal oxide catalysts or internals (5, 6) which are coated with the metal oxide catalyst. If desired, the reaction zones through which water flows continuously are spatially separated from the reaction zones which contain the catalyst material. Transfer from the high pressure to the low pressure stage (separator or polycondensation stage)
Das unter Druck stehende Reaktionsgemisch wird anschließend adiabatisch oder über eine Verdampferzone in eine Polykondensationsstufe (8) entspannt.The pressurized reaction mixture is then expanded adiabatically or via an evaporator zone into a polycondensation stage (8).
Adiabatische EntspannungAdiabatic relaxation
Die adiabatische Entspannung wird bevorzugt dann eingesetzt, wenn der Wassergehalt der Reaktionsmischung nicht mehr als 10 Gew.-%, bezogen auf die Gesamtmasse, beträgt.The adiabatic relaxation is preferably used when the water content of the reaction mixture is not more than 10% by weight, based on the total mass.
Bei der Entspannung kommt es zu einer Flashverdampfung des noch im Polymer befindlichen Wassers unter Nutzung der zuvor in der Polymerschmelze gespeicherten Reaktions- bzw. Eigenwärme. Im Gegensatz zu der herkömmlichen Verdampfung des Wassers an einer Wärmetauscherfläche können bei der Flashverdampfung aus der Polymermatrix keine Ausscheidungen an Wärmetauscherflächen und sonstigen Apparateoberflächen stattfinden. Eine Belagbildung durch organische oder anorganische Ausscheidungen wird vermieden. Zudem wird die im Prozeß freigesetzte Wärme direkt zur Wasserverdampfung genutzt, was eine weitere Energie- und Kostenersparnis bewirkt. Eine Abkühlung des Reaktionsgemisches ist zudem erwünscht, da das Polykondensationsgleichgewicht mit sinkender Temperatur auf die Seite des höhermolekularen Produkts verschoben wird. Der bei der Entspannung freigesetzte Wasserdampf enthält flüchtige Bestandteile wie das Aminonitril-Monomere und Oligomere. Durch die Rektifikation über eine Kolonne (9) kann der Wasserdampf aus dem System entfernt, und die organischen Bestandteile können in den Prozeß zurückgeführt werden. Eintrag in die zweite Reaktionsstufe über eine VerdampferzoneDuring the expansion, there is a flash evaporation of the water still in the polymer, using the reaction or inherent heat previously stored in the polymer melt. In contrast to the conventional evaporation of the water on a heat exchanger surface, no flashings can take place on the heat exchanger surfaces and other apparatus surfaces during flash evaporation from the polymer matrix. The formation of deposits through organic or inorganic precipitates is avoided. In addition, the heat released in the process is used directly for water evaporation, which results in further energy and cost savings. A cooling of the reaction mixture is also desirable since the polycondensation equilibrium is shifted to the side of the higher molecular weight product as the temperature drops. The water vapor released during the expansion contains volatile constituents such as the aminonitrile monomer and oligomer. Rectification via a column (9) removes the water vapor from the system and the organic constituents can be returned to the process. Entry into the second reaction stage via an evaporator zone
Im Fall eines hohen Wasseranteils im Reaktionsgemisch (>10 Gew.-%), das in die zweite Polykondensationsstufe eingetragen werden soll, ist der Einsatz einer Verdampferzone (7) vorteilhaft. Die im Reaktionsgemisch vorliegenden flüchtigen, niedermolekularen Komponenten wie Wasser und Ammoniak können dort in die Gasphase übertreten. Zudem gewährleistet die Verdampfungszone einen ausreichenden Wärmeeintrag in die Reaktionsmischung, so daß die durch Wasserverdampfung einsetzende Abkühlung der Mischung kompensiert werden kann.If there is a high proportion of water in the reaction mixture (> 10% by weight) which is to be introduced into the second polycondensation stage, the use of an evaporator zone (7) is advantageous. The volatile, low-molecular components such as water and ammonia present in the reaction mixture can pass into the gas phase there. In addition, the evaporation zone ensures a sufficient heat input into the reaction mixture, so that the cooling of the mixture which begins due to water evaporation can be compensated for.
Die Temperaturen in der Verdampferzone betragen 230 bis 320°C, bevorzugt 250 bis 290°C, die Verweildauer ist üblicherweise kleiner als 5 Minuten und beträgt vorzugsweise weniger als 60 Sekunden. Die Verdampferzone ist vorteilhaft als Röhrenbündel (7) ausgebildet, wobei die Röhren gewünschtenfalls in axialer Richtung periodisch wiederkehrende Querschnittsverengungen aufweisen.The temperatures in the evaporator zone are 230 to 320 ° C., preferably 250 to 290 ° C., the residence time is usually less than 5 minutes and is preferably less than 60 seconds. The evaporator zone is advantageously designed as a tube bundle (7), the tubes optionally having periodically recurring cross-sectional constrictions in the axial direction.
Bevorzugt wird das Reaktionsgemisch nach der Verdampferzone in eine Stoffaustauschzone geleitet, wobei die Druck- und Temperaturbedingungen der Verdampfungszone beibehalten werden. Der Stoffaustausch zwischen flüssiger und gasförmiger Phase kann hier fortgesetzt und die Ammoniakabscheidung verbessert werden. Die röhrenförmige Stoffaustauschzone enthält Einbauten, zum Beispiel Füllkörper wie Raschigringe, Metallringe und Füllkörper aus Drahtnetz, um eine große Oberfläche zur Verfügung zu stellen. Als Stoffaustauschzonen können auch andere bekannte Verdampferapparate wie Umlaufverdampfer und Dünnschichtverdampfer, beispielsweise Filmextruder oder Ringscheibenreaktoren, eingesetzt werden.After the evaporator zone, the reaction mixture is preferably passed into a mass transfer zone, the pressure and temperature conditions of the evaporation zone being maintained. The mass transfer between the liquid and gaseous phases can continue here and the ammonia separation can be improved. The tubular mass transfer zone contains internals, for example fillers such as Raschig rings, metal rings and fillers made of wire mesh, in order to provide a large surface area. Other known evaporator apparatuses, such as circulation evaporators and thin-film evaporators, for example film extruders or annular disk reactors, can also be used as mass transfer zones.
Erfindungsgemäß sind die Füllkörper mit den o.g. Katalysatorkomponenten beschichtet, oder Katalysatorgranulat wird direkt als Füllkörper eingesetzt. Der Um- satz von Nitril- und Säureamidgruppen im Reaktionsgemisch kann auf diese Weise entscheidend verbessert werden. NachkondensationAccording to the invention, the packing is coated with the above-mentioned catalyst components, or catalyst granules are used directly as packing. The conversion of nitrile and acid amide groups in the reaction mixture can be decisively improved in this way. postcondensation
Das nach dem Entspannen bzw. nach dem Verdampfen in der Verdampferzone erhaltene Produkt unterwirft man in mindestens einer anschließenden Reaktions- stufe (8), der sogenannten Abscheider- bzw. Polykondensationsstufe, die ge- wünschtenfalls ebenfalls heterogene Katalysatoren enthält, einer Nachpolymerisation bzw. -kondensation gegebenenfalls unter vermindertem Druck, gemäß bekannten Verfahren. Der Druck in dieser Abscheidezone liegt in der Regel im Bereich von 0,1 mbar bis 5 bar, bevorzugt im Bereich von 100 bis 1500 mbar, die Temperatur in der Schmelze beträgt 230 bis 320, bevorzugt 240 bis 290 und besonders bevorzugt 250 bis 270°C.The product obtained after the expansion or after evaporation in the evaporator zone is subjected to post-polymerization or condensation in at least one subsequent reaction stage (8), the so-called separator or polycondensation stage, which, if desired, also contains heterogeneous catalysts optionally under reduced pressure, according to known methods. The pressure in this separation zone is generally in the range from 0.1 mbar to 5 bar, preferably in the range from 100 to 1500 mbar, the temperature in the melt is 230 to 320, preferably 240 to 290 and particularly preferably 250 to 270 ° C.
Vorteilhaft werden die hier in die Gasphase freigesetzten Komponenten zusammen mit den Dämpfen aus der Verdampfungs- und Stoffaustauschzone in einer Kolonne (9) rektifiziert. Die Kolonne kann beispielsweise unter den gleichen Druckbedingungen wie die Verdampferzone betrieben werden. Die rektifizierten Ammoniak- und Wasserdämpfe werden am Kopf der Kolonne entnommen und kondensiert. Das erhaltene Wasser kann ebenso wie die im Kolonnensumpf niedergeschlagenen niedermolekularen Bestandteile bzw. Oligomere dem Edukt- ström zugeführt (zurückgeführt) werden.The components released here in the gas phase are advantageously rectified together with the vapors from the evaporation and mass transfer zone in a column (9). The column can be operated, for example, under the same pressure conditions as the evaporator zone. The rectified ammonia and water vapors are removed at the top of the column and condensed. The water obtained, like the low molecular weight constituents or oligomers deposited in the column bottom, can be fed (returned) to the educt stream.
Dreistufige Ausführungsform (siehe Figur 2)Three-stage embodiment (see Figure 2)
Das Aminonitril/Wassergemisch wird analog zur zweistufigen Ausfuhrungsform in einer ersten Stufe (3), die der vorstehenden Beschreibung entspricht, umgesetzt. Bevorzugt wird diese Stufe in der dreistufigen Ausfuhrungsform jedoch ohne den Einsatz einer Katalysatorschüttung betrieben.The amino nitrile / water mixture is implemented analogously to the two-stage embodiment in a first stage (3), which corresponds to the above description. This stage is preferably operated in the three-stage embodiment, however, without the use of a catalyst bed.
Die Katalysatorschüttung befindet sich in einer nachgeschalteten zweiten Reakti- onsstufe (13), beispielsweise einem Rohreaktor, in dem der Druck so eingestellt wird, daß das Reaktionsgemisch einphasig-flüssig vorliegt. Vorteilhaft ist der Einsatz einer Pumpe (12) zum Eintrag der Reaktionsmischung in den Rohrreaktor, um die Einphasigkeit des Systems zu garantieren. Die Temperaturen im Rohrreaktor betragen 200 bis 320°C, bevorzugt 210 bis 290°C und besonders bevorzugt 220 bis 260°C.The catalyst bed is located in a downstream second reaction stage (13), for example a tubular reactor, in which the pressure is adjusted so that the reaction mixture is in a single-phase liquid. It is advantageous to use a pump (12) to introduce the reaction mixture into the tubular reactor, to guarantee the single phase of the system. The temperatures in the tubular reactor are 200 to 320 ° C, preferably 210 to 290 ° C and particularly preferably 220 to 260 ° C.
Das Produkt aus der zweiten Stufe wird dann wiederum analog zur zweistufigen Ausfuhrungsform entweder adiabatisch oder über Verdampfer- und Stoffaustauschzonen (7) in eine dritte Stufe (8) zur Wasserabscheidung und Nachkondensation übertragen.The product from the second stage is then again transferred, analogously to the two-stage embodiment, either adiabatically or via evaporator and mass transfer zones (7) to a third stage (8) for water separation and post-condensation.
Additive und ZusatzstoffeAdditives and additives
Als übliche Zusatz- und Füllstoffe kann man Pigmente, wie Titandioxid, Sili- ciumdioxid oder Talk, Kettenregler, wie aliphatische und aromatische Carbon- und Dicarbonsäuren, wie Propionsäure oder Terephthalsäure, Stabilisatoren, wie Kupfer(l)halogenide und Alkalimetallhalogenide, Nukleierungsmittel, wie Magnesiumsilikat oder Bornitrid, Katalysatoren, wie phosphorige Säure, sowie Antioxidantien in Mengen im Bereich von 0 bis 5 Gew.-%, bevorzugt von 0,05 bis 1 Gew.-%, bezogen auf die Gesamtmenge an Monomeren, einsetzen. Die Additive setzt man in der Regel vor dem Granulieren und vor, während oder nach, bevorzugt nach der Polymerisation zu. Besonders bevorzugt werden die Additive dem Reaktionsgemisch erst nach Durchlaufen der Reaktionszonen, die die heterogenen Katalysatoren enthalten, zugesetzt.Pigments such as titanium dioxide, silicon dioxide or talc, chain regulators such as aliphatic and aromatic carboxylic and dicarboxylic acids such as propionic acid or terephthalic acid, stabilizers such as copper (I) halides and alkali metal halides, nucleating agents such as magnesium silicate can be used as customary additives and fillers or boron nitride, catalysts, such as phosphorous acid, and antioxidants in amounts in the range from 0 to 5% by weight, preferably from 0.05 to 1% by weight, based on the total amount of monomers. The additives are generally added before the granulation and before, during or after, preferably after the polymerization. The additives are particularly preferably added to the reaction mixture only after passing through the reaction zones which contain the heterogeneous catalysts.
Weiterverarbeitungprocessing
Das erfindungsgemäß erhaltene Polymer (11) kann dann nach üblichen Verfahren weiter verarbeitet werden, beispielsweise kann es nach üblichen Methoden stückig gemacht werden, indem man es in Form von Schmelzprofilen austrägt, anschließend durch ein Wasserbad leitet und hierbei abkühlt und dann granuliert. Das Granulat kann man dann nach an sich bekannten Methoden extrahieren und anschließend oder gleichzeitig zu hochmolekularen Polylactam umsetzen. Die Extraktion kann beispielsweise mit Wasser oder wäßriger Caprolactamlösung er- folgen. Eine weitere Möglichkeit ist die Gasphasenextraktion, wie sie beispielsweise in EP-A-0284 968 beschrieben ist. Die gewünschte Viskositätszahl des Endproduktes liegt in der Regel im Bereich von 120 bis 350 ml/g. Sie kann in an sich bekannter Weise eingestellt werden.The polymer (11) obtained according to the invention can then be processed further by customary processes, for example it can be made into pieces by customary methods by discharging it in the form of melt profiles, then passing it through a water bath and cooling it and then granulating it. The granules can then be extracted by methods known per se and subsequently or simultaneously converted into high molecular weight polylactam. The extraction can be carried out, for example, with water or an aqueous caprolactam solution. consequences. Another possibility is gas phase extraction, as described for example in EP-A-0284 968. The desired viscosity number of the end product is usually in the range from 120 to 350 ml / g. It can be set in a manner known per se.
Für weitere Füllstoffe, Monomergemische, Katalysatoren und Aufarbeitungen wird auf die DE-A-197 09 390 verwiesen.For further fillers, monomer mixtures, catalysts and refurbishments, reference is made to DE-A-197 09 390.
Die nachstehenden Beispiele dienen der näheren Erläuterung der Erfindung und zeigen, daß die Erfindung die Herstellung von Polyamiden mit hoher Viskosität ermöglicht.The following examples serve to explain the invention in more detail and show that the invention enables the production of polyamides with high viscosity.
BeispieleExamples
Analytikanalytics
Die sogenannte relative Viskosität (RV) des extrahierten Produktes als Maß für den Molekulargewichtsaufbau und Polymerisationsgrad wird in 1 Gew.-%iger Lösung in 96%iger Schwefelsäure bei 25°C mittels Viskosimeter nach Ubbelohde bestimmt.The so-called relative viscosity (RV) of the extracted product as a measure of the molecular weight build-up and degree of polymerization is determined in a 1% strength by weight solution in 96% strength sulfuric acid at 25 ° C. using a Ubbelohde viscometer.
Zur Extraktion werden 100 Gew.-Teile Polymer mit 400 Gew.-Teilen vollentsalztem Wasser von 100°C für eine Dauer von 32 Stunden unter Rückfluß gerührt bzw. extrahiert und nach Entfernen des Wassers milde, d.h. ohne die Gefahr einer Nachkondensation, bei einer Temperatur von 100°C für eine Zeitdauer von 20 Stunden im Vakuum getrocknet.For extraction, 100 parts by weight of polymer are stirred or extracted with 400 parts by weight of deionized water at 100 ° C. for 32 hours under reflux and, after removal of the water, mild, i.e. without the risk of post-condensation, dried at a temperature of 100 ° C for a period of 20 hours in a vacuum.
Diskontinuierliche Ausführungsformen der BeispielverfahrenDiscontinuous embodiments of the example methods
Die Verfahrensbeispiele 1, 2, 3 und 4 wurden diskontinuierlich in einem 11- Autoklaven durchgeführt. 1. Verfahrensstufe (Hochdruck)Process examples 1, 2, 3 and 4 were carried out batchwise in an 11-autoclave. 1st process stage (high pressure)
Nach dem Einfüllen der Reaktanden wird der Autoklav verschlossen, entlüftet und mehrmals mit Stickstoff gespült. Nach dem Aufheizen auf die gewünschte Reaktionstemperatur wird dem Reaktionsgemisch durch die Austragsöffnung des Kessels mit Hilfe einer Kolbenpumpe kontinuierlich Wasser zugeführt. Ein Ventil an der Brüdenleitung regelt hierbei den Kesselinnendruck. Der obere Teil des Reaktionsvolumens wird gerührt.After the reactants have been introduced, the autoclave is closed, vented and flushed several times with nitrogen. After heating to the desired reaction temperature, water is continuously fed to the reaction mixture through the discharge opening of the boiler with the aid of a piston pump. A valve on the vapor line regulates the internal boiler pressure. The upper part of the reaction volume is stirred.
2. Verfahrensstufe (Nachkondensation)2nd stage of the process (post-condensation)
Nach Ablauf der Reaktionszeit in der ersten Stufe wird die Wasserzufuhr unterbrochen und der Druck und die Temperatur im Reaktor werden innerhalb von 30 bis 60 Minuten auf die geforderten Werte zur Nachkondensation abgesenkt bzw. eingestellt. Die Polymerschmelze kann nach der Polykondensationsphase in ein Wasserbad strangformig ausgefahren, granuliert und getrocknet werden.After the reaction time in the first stage has ended, the water supply is interrupted and the pressure and the temperature in the reactor are reduced or set to the required values for post-condensation within 30 to 60 minutes. After the polycondensation phase, the polymer melt can be drawn out in a strand in a water bath, granulated and dried.
Für die Polymerisationsbeispiele in Gegenwart eines Festbettkatalysators wird Katalysatorgranulat, hergestellt aus Titandioxid von Finnti, Typ S150, mit einem Durchmesser von 4 mm und einer Länge zwischen 5 und 20 mm eingesetzt. Das Titandioxid liegt in der Anatas-Modifikation vor und wird mit Hilfe von Sieben im Autoklaven fixiert bzw. vom austretenden Produktstrom getrennt.For the polymerization examples in the presence of a fixed bed catalyst, catalyst granules made from Finnti titanium dioxide, type S150, with a diameter of 4 mm and a length between 5 and 20 mm are used. The titanium dioxide is present in the anatase modification and is fixed in the autoclave with the aid of sieves or separated from the emerging product stream.
Die Zusammensetzung der Eduktmischungen, die Verfahrensbedingungen und die relativen Viskositäten der erhaltenen Polyamide sind nachstehend in Tabelle 1 aufgelistet. Tabelle 1: Diskontinuierliche Ausführungsformen der BeispielverfahrenThe composition of the reactant mixtures, the process conditions and the relative viscosities of the polyamides obtained are listed in Table 1 below. Table 1: Discontinuous embodiments of the example methods
VWD: Verweildauer TiO2: Granulat aus Titandioxid * Molares ACN/ Wasser- Verhältnis RV: relative Viskosität VWD: residence time TiO 2 : granules of titanium dioxide * molar ACN / water ratio RV: relative viscosity

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Polyamiden aus Aminonitrilen und Wasser durch1. Process for the preparation of polyamides from aminonitriles and water
(1) Umsetzung von Aminonitrilen mit Wasser bei einer Temperatur im Bereich von 180 bis 350°C und einem Druck im Bereich von 30 bis 120 bar, der so eingestellt wird, daß neben einer flüssigen Phase eine gasförmige Phase vorliegt, in einer ersten Reaktionsstufe,(1) reaction of aminonitriles with water at a temperature in the range from 180 to 350 ° C. and a pressure in the range from 30 to 120 bar, which is adjusted so that a gaseous phase is present in addition to a liquid phase, in a first reaction stage,
(2) Entspannung des in der ersten Reaktionsstufe erhaltenen Reaktionsgemisches über eine Verdampferzone oder adiabatisch unter Entfernung von Wasser und Ammoniak in eine zweite Reaktionsstufe und (3) Nachkondensation in der zweiten Reaktionsstufe bei einem Druck im(2) expansion of the reaction mixture obtained in the first reaction stage via an evaporator zone or adiabatically with removal of water and ammonia in a second reaction stage and (3) post-condensation in the second reaction stage at a pressure in the
Bereich von 0,1 mbar bis 5 bar und einer Temperatur im Bereich 230 bis 320°C.Range from 0.1 mbar to 5 bar and a temperature in the range 230 to 320 ° C.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Umsetzung in der ersten Reaktionsstufe in Gegenwart von heterogenen Katalysatoren durchgeführt wird.2. The method according to claim 1, characterized in that the reaction in the first reaction stage is carried out in the presence of heterogeneous catalysts.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zwischen der ersten Reaktionsstufe, in der die Umsetzung in Abwesenheit des Katalysators durchgeführt wird, und der Entspannung eine weitere Reaktionsstufe vorgesehen ist, in der das in der ersten Reaktionsstufe erhaltene Reaktionsgemisch in Gegenwart von heterogenen Katalysatoren bei einer Temperatur im Bereich von 200 bis 320 °C und einem Druck, bei dem das Reaktionsgemisch einphasig-flüssig vorliegt, umgesetzt wird.3. The method according to claim 1, characterized in that between the first reaction stage in which the reaction is carried out in the absence of the catalyst, and the relaxation, a further reaction stage is provided in which the reaction mixture obtained in the first reaction stage in the presence of heterogeneous catalysts at a temperature in the range of 200 to 320 ° C and a pressure at which the reaction mixture is in single-phase liquid is reacted.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Katalysator ausgewählt ist aus Zirkonoxid, Aluminiumoxid, Magnesiumoxid, Ceroxid, Lanthanoxid, Titandioxid, ß-Zeolithen und Schichtsilikaten, die dotiert sein können.4. The method according to any one of claims 1 to 3, characterized in that the catalyst is selected from zirconium oxide, aluminum oxide, magnesium oxide, Cerium oxide, lanthanum oxide, titanium dioxide, β-zeolites and layered silicates, which can be doped.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß ein Titandioxid als Katalysator eingesetzt wird, das zu mindestens 70 Gew.-% in der Anatas- Modifikation vorliegt.5. The method according to claim 4, characterized in that a titanium dioxide is used as a catalyst, which is present at least 70 wt .-% in the anatase modification.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß in der ersten Reaktionsstufe Ammoniak und Wasser über eine Kolonne entfernt werden.6. The method according to any one of claims 1 to 5, characterized in that ammonia and water are removed via a column in the first reaction stage.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß auch das in der zweiten Reaktionszone erhaltene Wasser und Ammoniak in die Kolonne geführt werden.7. The method according to claim 6, characterized in that the water and ammonia obtained in the second reaction zone are fed into the column.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der ersten Reaktionsstufe kontinuierlich Wasser zugeführt wird. 8. The method according to any one of claims 1 to 7, characterized in that water is continuously fed to the first reaction stage.
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DE10114690A1 (en) * 2001-03-23 2002-09-26 Basf Ag Preparation of a polyamide comprises using a nitrile from 6-aminocapronitrile and adiponitrile in an aqueous reaction mixture and introducing an inert gas
DE10217433A1 (en) * 2002-04-18 2003-10-30 Basf Ag Inherently crosslinkable polyamides
DE10251798A1 (en) * 2002-11-07 2004-05-19 Bayer Ag Process for preparation of polyamide 6 by reaction of epsilon-caprolactam and water giving polyamide 6 with the smallest possible content of cyclic epsilon-caprolactam dimers
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PL2784102T3 (en) * 2013-03-26 2016-06-30 Uhde Inventa Fischer Gmbh Method and device for the continuous return of extract water in the polyamide production process
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Publication number Priority date Publication date Assignee Title
US4568736A (en) 1984-09-17 1986-02-04 The Standard Oil Company Preparation of polyamide from omega-aminonitrile with oxygen containing phosphorus catalyst
US5109104A (en) 1990-10-04 1992-04-28 E. I. Du Pont De Nemours And Company Preparation of polyamides from omega-aminonitriles
DE19709390A1 (en) 1997-03-07 1998-09-10 Basf Ag Improved production of polyamide from amino-nitrile and water
EP0922065B1 (en) * 1996-08-30 2002-11-20 Basf Aktiengesellschaft Process for producing polyamides from aminonitriles
DE19804023A1 (en) 1998-02-02 1999-08-05 Basf Ag Continuous process for the production of polyamides from aminonitriles
DE19804033A1 (en) * 1998-02-02 1999-08-05 Basf Ag Continuous process for the production of polyamides from aminonitriles
DE19804014A1 (en) * 1998-02-02 1999-08-05 Basf Ag Batch process for the production of polyamides from aminonitriles
DE19804020A1 (en) * 1998-02-02 1999-08-05 Basf Ag Process for the preparation of polyamides from aminonitriles
DE19846014A1 (en) * 1998-10-06 2000-04-13 Basf Ag Accelerator for the production of polyamides from aminonitriles
HUP0105495A2 (en) * 1999-02-11 2002-05-29 Basf Ag Method for producing polyamide 6 of a low extract content, high viscosity stability and low remonomerization rate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0148053A1 *

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